Medicinal and Process Chemistry Division, CSIR-Central Drug Research Institute, Lucknow 226031, India.
Molecular and Structural Biology Division, CSIR-Central Drug Research Institute, Lucknow 226031, India.
Org Biomol Chem. 2018 Jul 7;16(25):4623-4627. doi: 10.1039/c8ob01017j. Epub 2018 Jun 7.
A 1,6-conjugate addition reaction of the Seyferth-Gilbert reagent (SGR) to p-quinone methides is reported. This base-mediated protocol allows rapid access to diarylmethylated diazomethylphosphonates. The reaction proceeds under mild basic conditions, making it a practical approach for the synthesis of diarylmethylated diazomethylphosphonates with a broad substrate scope. Interestingly, the treatment of the conjugate adduct with a catalytic amount of rhodium acetate resulted in the 1,2-aryl migration of the rhodium carbenoid intermediate to generate the corresponding 1,2-diaryl alkenylphosphonates in excellent yields.
报道了 Seyferth-Gilbert 试剂（SGR）与对醌甲川的 1,6-共轭加成反应。该碱介导的方案允许快速获得二芳基甲基化重氮甲基膦酸酯。该反应在温和的碱性条件下进行，因此是合成具有广泛底物范围的二芳基甲基化重氮甲基膦酸酯的实用方法。有趣的是，用催化量的醋酸铑处理共轭加成物导致铑卡宾中间体的 1,2-芳基迁移，以优异的收率生成相应的 1,2-二芳基烯基膦酸酯。
